JPS62241925A - Curable polyene-polythiol resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in storage stability, curability, properties of a cured article, etc., and suitable for, e.g., paints, by using an alkenyl group-containing urethane (meth)acrylate and a compound having a plurality of mercapto groups in the molecule as essential components. CONSTITUTION:The titled composition is prepared by using an alkenyl group- containing urethane (meth)acrylate (A) of formula I (wherein R<1> is H or methyl, Z is a 2-8 C bivalent organic group, A is an a cyclic group derived from an compound of formula II, R3 is H, a 20 C or lower hydrocarbon group or the like, R<4> is a 20 C or lower alkenyl, B is an a cyclic group derived from a cyclic compound other than the compound of formula II, R<2> is a hydrocarbon group- containing organic compound other than the compound of formula III, l is 1-20, m is 0 or 1-20, p is 1-6, q is 0 or 1-5, r is 0 or 1-5 and Y is an isocyanate residue), e.g., a compound of formula IV and a compound (B) having a plurality of mercapto groups in the molecule (e.g., trimethylolethane trithioglycolate) as essential components.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyene-polythiol-based curable resin composition, and more specifically, it has excellent storage stability and physical properties of cured products, and can be used in paints, adhesives, and radiation-curable resin compositions. This invention relates to a novel polyene-polythiol-based curable resin composition useful for various uses such as mold resins and cast products.

[Conventional technology]

It is known that an unsaturated compound and a mercapto compound undergo a radical addition reaction. Therefore, compounds having at least two polymerizable unsaturated groups in one molecule (hereinafter sometimes abbreviated as polyene) and compounds having at least two mercapto groups in one molecule (hereinafter abbreviated as polythiol) It is well known that when a polymerization initiator is added to a mixture of 100% and 100% polyester, and the mixture is heated or irradiated with radiation, it hardens into a cured product.

[Problem that the invention seeks to solve]

However, mixtures of polyenes and polythiols
They are generally unstable and have the disadvantage of gradually thickening or gelling during storage.

In particular, adding a polymerization initiator will make it even more unstable.
It was difficult to store the product with the polymerization initiator added.

Methods to improve these drawbacks include adding a large amount of polymerization inhibitor, adding a special polymerization inhibitor, or mixing polyene and polythiol just before use to use them up in a short time. Although various attempts have been made, all of them have been unsatisfactory as they have impaired the curability and physical properties of the cured product.

Therefore, it is desired to develop a polyene-polythiol-based curable composition that has good storage stability and excellent curability and physical properties of the cured product. An object of the present invention is to provide a polyene-polythiol-based curable composition having the following properties.

[Means and effects for solving the problems] As a result of intensive study on the current situation, the present inventors have found that urethane (meth)acrylate containing at least one alkenyl group in one molecule and Novel polyenes consisting of compounds containing at least two mercapto groups
The present invention was achieved by discovering that a polythiol-based curable resin composition achieves the above object.

This polyene-polythiol-based curable resin composition can be used alone or in combination with other polymerizable unsaturated compounds, and if necessary, after adding a polymerization initiator, can be reacted. It has a wide range of uses, including radiation-curable resins, cast products such as lenses, hard coating agents, and inks.

The present invention is based on the general formula (1) [wherein R1 is a hydrogen atom or a methyl group,
Z represents a divalent organic group having 2 to 8 carbon atoms, (A) is a ring-opening group of alkenyl glycidyl ethers represented by the following general formula [II], and (B) is a ring-opening group of alkenyl glycidyl ethers represented by the following general formula (If). 7 represents an integer of 1 to 20, m represents 0 or an integer of 1 to 20, and alkenyl represented by (A) or (B) The arrangement of the ring-opening groups of glycidyl ethers or cyclic compounds is arbitrary, and R8 is a hydroxyl group-containing organic compound (excluding hydroxyl group-terminated (meth)acrylates represented by the following general formula [II]).
, p is an integer from 1 to 6, q is O or an integer from 1 to 5, r is O or an integer from 1 to 5, and is an integer, and Y is (p
+ q + r ) isocyanate group-containing organic compound residue. ] This relates to a polyene-polythiol-based curable resin composition containing as essential components an alkenyl group-containing urethane (meth)acrylate (a) and a compound having at least two mercapto groups in one molecule (b). be.

(Note) R'CH-CH-CH, No. 01
(II) [Wherein, R1 is a hydrogen atom or a (halo-substituted) hydrocarbon group having 20 or less carbon atoms, and R4 is an alkenyl group having 20 or less carbon atoms. ] CH, -C-C-0-Z-0i A-) ('B square H (1)
1m [In the formula, R1, Z, A%B%l and m are the same as above. ] To explain more briefly, the present invention provides a polyene-polythiol-based curable resin composition containing a polyene and a polythiol as essential components, in which a specific alkenyl group-containing urethane represented by the above general formula (1) is used as the polyene. The present invention relates to a novel polyene-polythiol-based curable resin composition characterized by using meth)acrylate (a).

The alkenyl group-containing urethane (meth)acrylate mark represented by the general formula (1) used in the present invention is, for example, the general formula (III) CH, -C-C' -0-Z -0A )-(B←H
(III) 1m (wherein R1 is a hydrogen atom or a methyl group,
2 represents a divalent organic group having 2 to 8 carbon atoms, and (A) has the general formula (fl) R"CH-CH-CH,OR'
(n) [In the formula, R8 is a hydrogen atom or has 2 carbon atoms
It is a (halo-substituted) hydrocarbon group having 0 or less carbon atoms, and R4 is an alkenyl group having 20 or less carbon atoms. ] represents the ring-opening group of the alkenyl glycidyl ether (a), (B) represents the ring-opening group of the cyclic compound (b) other than the alkenyl glycidyl ether represented by the above general formula [II], and l represents the ring-opening group of the alkenyl glycidyl ether (a) represented by An integer of 1 to 20, m represents 0 or an integer of 1 to 20, and the arrangement of the ring-opening group of the alkenyl glycidyl ether (a) or cyclic compound (b) represented by (A) or (B) is arbitrary. It is. ), a hydroxyl group-terminated (meth)acrylate (E) with the general formula Y-(-NGO) (wherein, Y
is a (pp+q+r +q+r)-valent isocyanate group-containing organic compound residue, and s p + q + r is an integer of 1 to 6. ] isocyanate group-containing organic compound (G
) and, if necessary, a hydroxyl group-terminated (meth)acrylate represented by the general formula (III) (E).

The hydroxyl group-terminated (meth)acrylate (E) represented by the general formula CIII) is, for example, the general formula (IV)
CH, -C-C-0-Z -OH (■) (in the formula,
R' is a hydrogen atom or a methyl group, and Z is a divalent organic group having 2 to 8 carbon atoms. ) Hydroxy (meta)
The hydroxyl group of the acrylate has the general formula [II]
The alkenyl glycidyl ethers represented by (a) and optionally a cyclic compound (bl) excluding the alkenyl glycidyl ethers represented by the general formula [II] can be obtained by an addition reaction method.

Specific examples of hydroxy(meth)acrylate represented by the general formula [■] include human tetraxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate,
Hydroxybutyl acrylate, hydroxybutyl methacrylate, diethylene glycol monoacrylate,
Examples include diethylene glycol monomethacrylate, hydroxycyclohexyl acrylate, and hydroxycyclohexyl methacrylate. These alone,
Alternatively, it can be used as a mixture.

The compound to be subjected to the addition reaction with the hydroxy(meth)acrylate is a cyclic compound other than the alkenyl glycidyl ethers (a) represented by the general formula (It) and, if necessary, the alkenyl glycidyl ethers represented by the general formula [■]. Selected from (b).

Examples of the (octoday-substituted) hydrocarbon group in the alkenyl glycidyl ether (a) K represented by the above general formula include an alkyl group having 20 or less carbon atoms, an alkenyl group, an aryl group, a hydrogenated aryl group, and an aralkyl group. or at least one hydrogen atom of those hydrocarbon groups
Examples include a halo-substituted hydrocarbon group in which each hydrogen atom is substituted with a halogen atom, and of course, all hydrogen atoms may be substituted with a halogen atom in the first group.

Examples of alkenyl glycidyl ethers (a) are:
Examples include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, and the like.

Cyclic compounds excluding alkenyl glycidyl ethers (b
) (hereinafter abbreviated as cyclic compound (b)). Examples of ethylene oxide, propylene oxide, 1
, 2-butylene oxide, 1,2-epoxydecane, 1
．． Alkylene oxides such as 2-epoxyhexadecane; butadiene, 1.
Alkenyl oxides such as 2-epoxy-5-hexene; phenylalkylene oxides such as styrene oxide; 1,5-cyclododecadiene-9-10
- hydrogenated aryl alkylene oxides such as epoxides, 1,2-epoxycyclododecane, etc.; ε-caprolactones such as 6-caprolactone, methyl-ε-caprolactone; tetrahydro-7rane; methyl glycidyl ether, propyl glycidyl ether Alkyl glycidyl ethers such as , butyl glycidyl ether; aryl glycidyl ethers such as phenyl glycidyl ether, cresyl glycidyl ether; and shrimp halohydrins such as epichlorohydrin, shrimp bromohydrin, etc.

General Formula [In the formula, Y is a (p+q+r)-valent isocyanate group-containing organic compound residue, and p+q+r is an integer of 1 to 6. ] Examples of the isocyanate group-containing organic compound (G) include monoisocyanates such as butyl isocyanate and incyanatoethyl methacrylate; 1,6-hexamethylene diisocyanate;
trimethylhexamethylene diisocyanate), 2.4-
or 2.6-) Polyisocyanates such as lylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, isophorone diisocyanate; the above polyisocyanates and polyols, polyether polyols, polyester polyols, ester diols, polyolefins Hydroxyl group-containing organic compounds such as polyols and polycarbonate polyols are mixed with isocyanate group number/
Prepolymers containing isocyanate groups at the ends obtained by reacting at a ratio of the number of hydroxyl groups greater than 1.0 can be mentioned.

The hydroxyl group-containing organic compound (K) used if necessary in the present invention contains at least one hydroxyl group capable of reacting with an isocyanate group other than the human tetraxyl group-terminated (meth)acrylate (E). Any organic compound can be used without particular restrictions. Examples of hydroxyl group-containing organic compounds (■) include polyols such as butanediol and trimethylolpropane; polyether polyols such as diethylene glycol and polyethylene glycol; polyols such as butanediol and triethylene glycol, and maleic anhydride. Polyester polyols obtained by reacting polyhydric carboxylic acids such as 2,2-dimethyl-3- with a ratio of hydroxyl groups/carboxyl groups greater than 1.0;
Ester diols such as hydroxyprobyl-2,2-dimethyl-3-hydroxyprobionate; polyolefin polyols such as polybutadiene polyol; such as the reaction product of 1,6-hexanediol and ethylene carbonate. Polycarbonate polyols: Addition of cyclic compounds such as ethylene oxide, epichlorohydrin, pryl glycidyl ether, C-caprolactone, etc. alone or in mixture to the above polyols, polyether polyols, polyester polyols, ester diols, polyolefin polyols or polycarbonate polyols. Hydroxyl group-containing compounds obtained by cycloaddition reaction; aliphatic-hydric alcohols such as methanol and ethanol; (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether; unsaturated acid partial esterification products of the above polyol compounds , for example, 1,6-hexanediol mono(meth)acrylate, pe/taerythritol tri(meth)acrylate; ring-opening adduct of lactones such as ε-caprolactone to hydroxyalkyl(meth)acrylate; having an epoxy group Examples include addition reaction products between a compound and an unsaturated acid.

A known production method can be used to produce the alkenyl group-containing urethane (meth)acrylate (a) used in the present invention. That is, the reaction of the hydroxyl group-terminated (meth)acrylate (E) represented by the general formula [■] with the isocyanate group-containing organic compound (G), or the reaction of the hydroxyl group-terminated (meth)acrylate (E) represented by the general formula (III) ( E) and a hydroxyl group-containing organic compound (K
) and a polyicanate group-containing organic compound [a compound containing two or more isocyanate groups in one molecule among the isocyanate group-containing organic compounds (G)].

The ratio of these raw materials may be charged depending on the alkenyl group-containing urethane (meth)acrylate (a) to be obtained, but usually the ratio of the number of isocyanate groups/the number of hydroxyl groups is in the range of 1.0±0.1. You can prepare it according to the ratio.

Examples of the compound (b) having at least two mercapto groups in one molecule used in the present invention include esters of a mercapto compound having a carboxyl group and a polyhydric alcohol, such as trimethylolethane trithioglycolate;
Trimethylolethane trithiopropionate, trimethylolethane trithioglycolate, trimethylolpropane trithioprobionate, pentaerythritol tetrathioglycolate, pentaerythritol tetrathioprobionate, ethylene glycol dithioglycolate, ethylene glycol dithioprobionate ,
Polyethylene glycol dithioglycolate, polyethylene glycol dithioprobionate, dipentaerythritol hexathioglycolate, dipentaerythritol hexathioprobionate; aliphatic polythiols such as dimercapto diethyl ether, dimercaptopropane, dimercaptohexane; aromatic Group polythiols, such as xylylene dithiol: a reaction product of a polyepoxy compound and hydrogen sulfide; a reaction product obtained by the reaction of a polyepoxy compound and thioglycolic acid; a compound having two or more unsaturated cycloacetal groups; Examples include reaction products obtained by reaction with hydrogen sulfide; esters of thioalcohols and polyvalent carboxylic acids; polyvalent thiophenols and polyvalent thiobisphenols. These can be used alone or as a mixture of the four.

The polyene-polythiol-based curable resin composition of the present invention comprises alkenyl group-containing urethane (meth)acrylate (a) represented by the general formula (1) and a compound (ro) having at least two mercapto groups in one molecule. ) as an essential component, but if necessary, a compound (c) having a polymerizable unsaturated group other than the alkenyl group-containing urethane (meth)acrylate (a) may be used in combination to form the polyene-polythiol system of the present invention. It can also be made into a curable resin composition.

Examples of the compound C→ having a polymerizable unsaturated group, which is optionally used in the present invention, include styrene, α-methylstyrene, acrylonitrile, (meth)acrylamide, diacetone acrylamide, N-methyl(meth)acrylamide, N -Methylol (meth)acrylamide, N-
Vinylpyrrolidone, diallyl phthalate, allyl glycidyl ether, (meth)acrylic acid, alkyl (meth)acrylates such as methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, methoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate Acrylate, dibromopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-
Hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol Di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trishydroxyethyl isocyanurate tri( meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyl Oxyethyl (meth)acrylate, silicone (
Polyester (meth)acrylate, amide (meth)acrylate, phosphoric acid (meth)acrylate, polyester obtained by the reaction of (meth)acrylic acid, glycols, and polybasic acid.
meth)acrylate, epoxy(meth)acrylate obtained by the reaction of (meth)acrylic acid with an epoxy compound, isocyanate group-containing compound and hydroxyalkyl (
Examples include urethane (meth)acrylate obtained by reaction with meth)acrylate, carboxyl group-containing (meth)acrylate obtained by reaction of carboxylic acid anhydride and hydroxyalkyl (meth)acrylate, etc.
These can be used alone or as a mixture. Furthermore, various polymers (for example, unsaturated polyester, epoxy, polyamide, acrylic, polyvinyl alcohol, etc.), organic solvents, fillers, tackifiers, stabilizers, plasticizers, and leveling agents are added as necessary. agents, dyes, pigments,
A polymerization inhibitor or the like can also be used in combination.

Alkenyl group-containing urethane represented by general formula (1) (
Mixing of the meth)acrylate (2) and the compound (2) having at least two mercapto groups in one molecule may be carried out at room temperature or in a heated state by stirring, mixing, or the like.

Alkenyl group-containing urethane (meth)acrylate (a)
The mixing ratio of the polymerizable unsaturated group in the compound (2) and the mercapto group in the compound (2) is not particularly limited, and is usually from 1:0.1 to 1:0.1 in terms of equivalent ratio.
The ratio is 1:3, preferably l:0.5 to 1:2.

The compositions of the present invention are generally cast or applied to a substrate and then cured. In order to cure the composition of the present invention, the composition may be heated or irradiated with radiation such as ultraviolet rays or electron beams, and in particular, it can be cured without adding a radical polymerization initiator or a photopolymerization initiator. I can do it.

However, a radical polymerization initiator or a photopolymerization initiator can also be used if necessary.

Examples of the radical polymerization initiator include benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cyclohexanone peroxide, t-butylhydride tetraperoxide, di-t-butyl peroxide, di-t-amyl peroxide, and dicumyl peroxide. , t-butyl perbenzoate, azobisin butyronitrile, etc. can be used, and if necessary, a radical polymerization accelerator such as cobalt octenoate, cobalt naphthenate, iron octenoate, manganese octenoate, vanadium octenoate, etc. can be used. Organic metal salts of , organic amines such as N,N-dimethylaniline, etc. can be used in combination.

Examples of photopolymerization initiators include benzoin, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin alkyl ethers; benzophenone, Michler's ketone, and methyl-0-benzoyl benzoate and other benzophenones; acetophenone, trichloroa-7tophenone, 2, 2-jethoxyacetophenone, pt-butyltrichloroacetophenone, 2.
Acetophenones such as 2-dimethoxy-2-phenylacetophenone, p-dimetelaminoacetophenone; Thioxanthone such as xanthone, thioxanthone, 2-chlorothioxanthone, 2-inglobilteoxanthone; benzyl, 2-ethylanthraquinone, methyl -benzoylformate, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 2-hydroxy-4'-isopropyl-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, tetramethylthiuram monosulfide, allyl diazonium salt can be used. If necessary, a sensitizer such as an amine compound, a sulfur compound, a phosphorus compound, etc. may be used in combination. These may be used alone or in combination.

Furthermore, radiation curing and heat curing can also be used together.

〔Effect of the invention〕

The polyene-polythiol curable resin composition of the present invention has good storage stability, excellent curability and adhesion to substrates, and has good physical properties of the cured product such as hardness of the cured product obtained by curing. It can be used in a wide range of applications such as adhesives, paints, adhesives, radiation-curable resins, pottery products, hard coating agents, and inks.

〔Example〕

Next, the present invention will be explained by examples, but the present invention is not limited by these examples.

Note that parts in the examples are parts by weight.

Reference Example 1 2-hydroxyethyl methacrylate 19 was placed in a reaction vessel equipped with a thermometer, dropping funnel, reflux condenser, and stirrer.
5 parts (1.5 moles), 0.21 parts of hydroquinone methyl ether as a polymerization inhibitor, and 2.83 parts of tungstosilicic acid as a catalyst, and 513 parts (4.5 moles) of allyl glycidyl ether were added at 50°C. After the dropwise addition took some time, the reaction was further maintained at 50° C. for 1 hour to complete the reaction. Next, 21 parts of powdered basic magnesium aluminum hydroxycarbonate hydrate as an adsorbent was added, stirred at 60°C for 30 minutes, and purified by pressure filtration to obtain a colorless transparent liquid reaction product ( Hereinafter, human tetraxyl group-terminated methacrylate (referred to as 11) 6
94 copies were obtained. As a result of analysis, the reaction product was a hydroxyl group-terminated methacrylate having the following structure.

CH.

CH, -C-COOCH, CH, 0-4CH, CHO)
rHCH! 0H, CH-CH.

Next, in a reaction vessel similar to the above, the obtained hydroxyl group-terminated methacrylate (11236 parts (0.5 eq.),
0.084 part of hydroquinone monomer ether as a polymerization inhibitor and 0.14 part of dibutyltin dilaure as a urethanization reaction catalyst were added, and then 2.
4-) 43.5 parts (0.5 equivalents) of lylene diisocyanate was added dropwise over 2 hours while maintaining the temperature at 60°C. By maintaining the mixture at 60° C. for an additional 4 hours, 279 parts of a reaction product (hereinafter referred to as urethane methacrylate (1)) was obtained. As a result of analysis, the reaction product was a urethane methacrylate having the following structure with a free isocyanate group content of 0.1% or less.

(However, C, H, represents a residue of 2,4-)lylene diisocyanate. ) Reference Example 2 In a reaction vessel similar to Reference Example 1, 13,236 parts (0.5 equivalents) of the hydroxyl-terminated methacrylate obtained in Reference Example 1, 0.14 part of hydroquinone monomethyl ether as a polymerization inhibitor, and urethanized 0.14 parts of dibutyltin dilaurate was charged as a reaction catalyst, and then 52.5 parts (0.5 equivalents) of trimethylhexamethylene diisocyanate (manufactured by Hüls) was added dropwise over 2 hours while stirring at 65°C. .

By further holding the temperature at 65°C for 3 hours, the reaction product-acid (hereinafter referred to as urethane methacrylate (2))288
I got the department. As a result of analysis, the reaction product was a urethane methacrylate having the following structure with a free isocyanate group content of 0.1% or less.

(However, C0H1, indicates the residue of trimethylhexamethylene diisocyanate.) Reference Example 3 In a reaction vessel similar to Reference Example 1, 139 parts (1°2 mol) of 2-hydroxyethyl acrylate and hydroquinone as a polymerization inhibitor were added. 410 parts (3.6 moles) of allyl glycidyl ether were added dropwise over 4 hours under stirring for 30 to 40 minutes, and then heated to 40°C. The reaction was completed by holding for 1 hour. Next, 11 parts of powdered magnesium silicate as an adsorbent was added, stirred at 40°C for 30 minutes, and purified by pressure filtration to produce a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-terminated acrylate (2)). Call.) 53
Got 9 copies. As a result of analysis, the reaction product was a hydroxyl group-terminated acrylate having the following structure.

CH, CHTSCH.

Next, in a reaction vessel similar to the above, 229 parts (0.5 equivalents) of the obtained hydroxyl group-terminated acrylate (2) and 0.5 parts of hydroquinone monomethyl ether as a polymerization inhibitor were added.
095 parts and 0.16 parts of dibutyltin dilaure as a urethanization reaction catalyst, and then 2.4 parts of
- 87 parts (1 equivalent) of tolylene diisocyanate at 60°C
After dropping for 2 hours, WK 4 hours, 60-6
It was maintained at 5°C.

Subsequently, 58 parts (0.5 equivalents) of 2-hydroxyethyl acrylate was added dropwise at 60°C over 2 hours, and the reaction product (
Hereinafter, it will be referred to as urethane acrylate (3). ) 374 copies were obtained. As a result of analysis, the reaction product was a urethane acrylate having the following structure with a free isocyanate group content of 0.1% or less.

(However, C〒H6 represents a 2.4-) lylene diisocyanate residue. ) Reference Example 4 In a reaction vessel similar to Reference Example 1, 174 parts (1.5 mol) of 2-hydroxyethyl acrylate, 0.26 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of tungstophosphoric acid as a catalyst were added. Preparation, internal temperature 30~
Allyl glycidyl ether 171 while keeping at 40℃
(1.5 mol) was added dropwise in 1 hour. After the dropwise addition was completed, the mixture was further aged at 40° C. for 1.5 hours. Next, 174 parts (3.0 mol) of propylene oxide was added at 30 to 40°C for 2 hours.
．． After dropping for 5 hours, the mixture was further aged at 40° C. for 2 hours to complete the reaction. Next, 11 parts of powdered magnesium silicate was added and purified by pressure-filtration to obtain 511 parts of a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-terminated acrylate (3)). As a result of analysis, the reaction product was a hydroxyl group-terminated acrylate having the following structure.

CH, CH■CH.

Next, in a reaction vessel similar to the above, 31,173 parts (O, S equivalent) of the obtained hydroxyl group-terminated acrylate was added, and 0.0% of hydroquinone monomethyl ether was added as a polymerization inhibitor.
11 parts of trimethylhexamethylene diisocyanate (manufactured by Hüls) and 0.11 parts of dibutyltin dilauret (dibutyltin dilauret) as a urethanization reaction catalyst were added, followed by stirring.
．． 5 parts (o, 5 parts) was added dropwise over 2 hours while maintaining the temperature at 60°C. By maintaining the temperature at 60°C for an additional 3 hours, a reaction product (hereinafter referred to as urethane acrylate (4)) was produced.
225 copies were obtained. The free isocyanate group content of the reaction product was less than 0.1%.

Example 1 1160 parts of the urethane methacrylate obtained in Reference Example 1 and 40 parts of pentaerythritol tetra(3-mercaptopropionate) were added, and the viscosity (25°C, E-type viscometer, manufactured by Tokyo Keiki) was 1310 cvsr:; Fourteen hours of the resin composition (1) of the present invention was prepared.The obtained resin composition (
11 was applied to a thickness of VCl 5μ on a steel plate panel, and
When the panel was irradiated using a W/AN high-pressure mercury lamp from a distance of 1 ocIIL while moving the panel at a conveyor speed of 2 m/min, a tack-free cured coating was obtained with one irradiation. Furthermore, when we examined the performance of the obtained cured coating film, we found that the pencil hardness was 5H and the adhesion was 100.
/Zoo.

In addition, the performance of the cured coating film was measured by the following method.

Pencil hardness: JIS K 5400 method Adhesion: Using a cutter knife on the coating film at 10°C m x 10
100 stitches were cut in an area of m, pressure-bonded with cellophane tape, and then vigorously peeled off. The state of peeling of the stitches was observed and expressed as 100 - (number of peeled stitches)/100.

won.

Comparative Example 1 40 parts of triallylisocyanurate and 60 parts of pentaerythritol tetra(3-mercaptopropionate)
The viscosity (25°C, E-type viscometer) was 389 cp.
Comparative composition (1), which is s, was prepared. When the obtained comparative composition (1) was left at room temperature, it gradually thickened and gelled completely in 3 days.

The results obtained in Example 1 and Comparative Example 1 show that the resin composition of the present invention has excellent storage stability.

Examples 2 to 5 Urethane (meth)acrylate obtained in Reference Examples 1 to 4) (
11 to (4), 2 parts of benzyl dimethyl ketal (manufactured by Ciba Geigy, Irgacure 651) was added to each of the mixtures obtained by blending polythiol and a compound having a polymerizable unsaturated group with the composition shown in Table 1. In addition, resin compositions (2) to (5) of the present invention were prepared. Using each of the obtained resin compositions (2) to (5), the curability of the coating film was examined in the same manner as in Example 1, and all showed tank-free cured coatings after one irradiation. was gotten. Furthermore, the performance of the obtained cured coating film was measured in the same manner as in Example 1, and the results are shown in Table 1.

Example 6 Urethane methacrylate (1) obtained in Reference Example 1 59
41 parts of trimethylolethane trimercaptopropionate and 0.2 parts of benzoyl peroxide were mixed to prepare a resin composition (6) of the present invention.

The obtained resin composition (6) was applied to a thickness of 30 μm on a steel plate panel and cured by holding at 80° C. for 3 hours. When the performance of the obtained cured coating film was examined in the same manner as in Example 1, the pencil hardness was 5H, and the adhesion was 1.
It was 00/100.

Claims (1)

[Claims] General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ [I] [However, in the formula, R^1 is a hydrogen atom or a methyl group, and Z is a dicarbonate having 2 to 8 carbon atoms. (A) represents a ring-opening group of alkenyl glycidyl ethers represented by the following general formula [II], (B) excludes alkenyl glycidyl ethers represented by the following general formula [II] represents a ring-opening group of a cyclic compound, l represents an integer of 1 to 20, m represents 0 or an integer of 1 to 20, and (A),
The arrangement of the ring-opening group of the alkenyl glycidyl ether or cyclic compound represented by (B) is arbitrary, and R^2 is a hydroxyl group-containing organic compound (however, the hydroxyl group terminal (meta) represented by the following general formula [III])
Excludes acrylate. ), p is an integer of 1 to 6, q is 0 or an integer of 1 to 5, r is 0 or an integer of 1 to 5, p+q+r is an integer of 1 to 6, , Y is a (p+q+r)-valent isocyanate group-containing organic compound residue. ] A polyene-polythiol-based curable resin composition containing as essential components an alkenyl group-containing urethane (meth)acrylate (a) represented by the formula (a) and a compound (b) having at least two mercapto groups in one molecule. (Note) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] [In the formula, R^3 is a hydrogen atom or a (halo-substituted) hydrocarbon group having 20 or less carbon atoms, and R^4 is a carbon number of 20 or less.
The following alkenyl groups. ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] [However, in the formula, R^1, Z, A, B, l, and m are the same as above. ]